Recent Developments in
6:2 Fluorotelomer Surfactants andFoam Stabilizers
Eduard Kleiner and Chang Jho
Dynax Corporation, NY USA
4Th Reebok Foam Seminar, Bolton, UK 6 – 7 July 20094Th Reebok Foam Seminar, Bolton, UK 6 – 7 July 2009
From
PFOS/PFOA Fluorosurfactants
to
6:2 Fluorotelomer Surfactants,
which biodegrade into
6:2 Fluorotelomer Sulfonate (6:2 FTS),
used as
Film Formers (Non-polymeric)
Fuel Repellents (Polymeric)
Foam Stabilizers (Polymeric)
4Th Reebok Foam Seminar, Bolton, UK 6 – 7 July 2009
From PFOS/PFOA to 6:2 Fluorotelomer Surfactants
Year Events Reference
1963
Tuve + Jablonsky, US NRL, 3M/NRL Collaboration
PFOS + PFOA type fluorosurfactants
Light Water + Purple K (Twin Agents) (no hydrocarbon surfactants)
MIL-F-23905 (11/1/63) (Fresh water only)
US 3,258,423 (filed 9/4/63)
GB 1,070,289 (filed 9/3/64)
1964Ratzer, Chemical Concentrates:
Use of Hydrocarbon Surfactants with fluorosurfactants in AFFF
Campobello Foam Meeting
(10/11-13/64), Published in
“Foam” Oct. 1964, Nr. 24
1967 USS Forrestal FireProtein Foam; 134 dead and
21 aircrafts destroyed
19693M Francen Patents:
Use of Hydrocarbon Surfactants with Fluorosurfactants in AFFF
US 3,562.156 (filed 6/12/69)
US 3,772,195 (filed 2/5/71):
Invalidated 1980
1969 MIL-F-24385 (6% AFFF) (Fresh & Seawater) Seawater tests introduced
1972–75
Atochem, France & Ciba-Geigy, USA:
6:2/8:2 and 6:2 FT-Surfacatants for AFFF Agents
Pilot plant production for AFFF agent tests at
Eau et Feu (Atochem) and Ansul (Ciba-Geigy)
“Forafac” (Atochem) and
“Lodyne” (Ciba-Geigy)
1978 DC-10 Crash Fire at LAX (First major use of 3M Light Water) 196 lives saved out of 200
1982–Large selections of 6:2 FT-Surfactants available to
AFFF agent producers
6:2 FT-surfactants:
C6 (~95 to 97%) + C4 & C8
1992 MIL-F-24385F (3% & 6% AFFF) 3% requirements introduced
USS Forrestal Fire – 29 July 1967
DC-10 Crash Fire at LAX – 1 March 1978
Environmental Studies of AFFF Agents
Sampling Site Source of AFFF Major Components1
2004 US Study (ground water)*
Naval Air Station, Fallon, NE 3M PFOS + PFOA
Tyndall AFB, FL 3M + Ansul PFOS + PFOA +
6:2 FTS2/4:2 & 8:2 FTS Wurtsmith AFB, MI 3M + Ansul
2008 Norwegian Study (soil)**
Mongstad Oil Refinery National Foam + 3M
PFOS + PFOA + 6:2 FTSSolberg Scandinavian AS 3M + DuPont(?)
Gardermoen Airport 3M + DuPont (?)
Rygge Air Station 3M PFOS + PFOA
*Jennifer Field, et. al., Environ. Sci. Technol. 2004, 38, 1828.**Norwegian Pollution Control Authority (SFT) Report (2008) 1PFOS and PFOA include other homologs.2Ansul AFFF derived from Lodyne fluorosurfactants (Ciba-Geigy) contained >95% 6:2 FT-surfactants. 6:2FTS was never used in AFFF agents.
Chemistry and Biodegradation of 6:2 Fluorotelomer Surfactants
Starting Material:
6:2 FT-Iodide
Type of
6:2 FT-Surfactants
Biodegradation Products*:
6:2 FT-Sulfonate (6:2 FTS)
*Based on environmental studies.??
C6F13CH2CH2-I
C6F13CH2CH2-SCH2- C6F13CH2CH2-SO2NH-
C6F13CH2CH2-SO3-
Foam Stabilizers for AR-AFFF/AR-FFFP Agents
Year Producer Foam Stabilizer AR-AFFF/AR-FFFP
1973 National Foam Polysaccharides (PS) 3x6 (High viscosity)
1990 Ciba-Geigy Lodyne K90’90*3x3 (Low viscosity)
AR-AFFF/AR-FFFP
1995 DynaxDX5011 6:2 Fluorotelomer Polymeric Surfactant
3x3 (Lower viscosity)
AR-AFFF & AR-FFFP
1998-99 DuPontForafac 1210*
Forafac 1268*
AR-FFFP
AR-AFFF
2000 Ciba Specialty Chem Lodyne 5100* AR-AFFF/AR-FFFP
2008 Dynax
DX5022Only 6:2 Fluorotelomer Foam Stabilizer that biodegrades to 6:2 FTS
3x3, 1x1, 0.5x0.5Development of semi-Newtonian AR-AFFF & AR-FFFP agents without PS
* Fluorotelomer polymeric surfactant
Fluorosurfactants for Fluoroprotein Foam Agents
Year Events
1968Chubb Fire introduces FP foams based on ICI Monflor MD 313:
Used by all FP agent producers.
1973 Regular Ministry Supply Contracts for Monflor MD 313-based FP agents
1980Ciba-Geigy introduces Lodyne K78’220(B) as drop-in replacement for Monflor MD 313.
ICI withdraws Monflor MD 313. K78’220(B) becomes THE ONLY GAME IN TOWN!
1990Lodyne K78’220B, an 8:2 FT-Surfactant, used as fuel repellent
in AFFF and FFFP agents.
2009Dynax DX2200 and Chemguard FS-220B (successors of Lodyne K78’220B):
STILL THE ONLY GAME IN TOWN!
2009 No Fluorine-free FP yet!!
2010/15 Phase-out period for 8:2 FT-Surfactants.
Note: Use levels of K78’220B (40%) in 3% FP: 0.3 – 0.6% (0.02 – 0.05%F)
Fluorosurfactants – Key Events 2002 – 2015
Year Events
2002 DuPont acquires the Atofina fluorotelomer business.
2003 Chemguard acquires Ciba Specialty Chemicals Lodyne fluorosurfactant business.
2004 Dynax introduces 6:2 Lodyne fluorosurfactants with > 99.5% C6
2005Chemguard introduces modified Lodyne fluorosurfactants with
~72% C6 and ~28% C8/C10.
2008 Dynax introduces DX5022, a second generation foam stabilizer.
2008DuPont announces introduction of short-chain fluorochemicals meeting
US EPA Global 2010/2015 PFOA Stewardship Program objectives.
2009 DuPont announces that 45 Capstone products are on the market by mid-2009
2010/15
EPA’s Global 2010/2015 PFOA Stewardship Program:
PFOA and higher homolog acids and their precursor chemicals should be reduced by
95% no later than 2010, and eliminated no later than 2015 from facility emissions and in
product content.
6:2 FT-Surfactants for Fire Fighting Foam Agents
Film Formers for AFFF/FFFP:
§ Non-polymeric
§ Fast equilibrating (high diffusion rate) (C6 vs C8)
§ Low equilibrium & dynamic surface tension (C6 vs C8)
Fuel Repellents for FP:
§ Polymeric (oligomeric)
§ Oleophobicity (fuel repellent) (C8 vs C6)
§ Slow equilibrating (low diffusion rate)
Foam Stabilizers for AR-AFFF/FFFP
§ Polymeric
§ Solvophobicity (solvent repellent)
§ Slow equilibrating (low diffusion rate)
4Th Reebok Foam Seminar, Bolton, UK 6 – 7 July 2009
Three Types of Fluorosurfactants
C6 vs C6/C8-based Non-ionic Fluorotelomer Surfactants
Dynamic Surface Tension Profile (0.1% actives in water)
US Air Force SBIR Phase 1 & 2 Contracts Awarded to Dynax in 1993 & 1994
“Improved Formulation of Fire Fighting Agents
for Hydrocarbon Fuel Fires”
Improved Extinguishment
+ Improved Foam Life and Burnback Resistance
+ Lower Levels of Fluorosurfactants
+ Lower Toxicity on Aquatic Life Forms
+ Elimination of Butyl Carbitol (SARA Title III Section 313)
= Environmentally More Benign (EMB) AFFF Agents
3% AFFF Agents on US QPL List in 1993:
Highest Fluorine Content: 1.8%F (3M Light Water FC-203CF)
Lowest Fluorine Content: 0.85%F (NF Air-O-Water 3EM)
Proposed MIL-F-24385 Specification Changes
Maximum Fluorine Content 0.85%
Spreading Coefficient Increase (3.0 àààà 5.0)
Toxicity, LC50, mg/L (Min) Increase (50 àààà 750)
COD, mg/L (Max) Decrease (1,000K àààà 600K)
BOD20/COD (Min) Leave at 0.65*
*Subject to definition of BOD/COD ratio
In 1993, the issues of PFOS/PFOA and C6 vs C8/C10 telomer type
fluorosurfactants did not exist.
3% AFFF Agents Solution MIL-F-24385F Proposed Spec*
Foam Expansion (min)3.0%1.5%
5.0None
6.56.0
¼ Drain Time (min, min)3.0%1.5%
2.5None
4.03.0
28 ft2 Fire Tests (Fresh & Seawater)
Extinguishment time (sec, max)3.0%1.5%
3045
Delete40
Burnback (sec, min) 3.0%1.5%
360300
Delete360
50 ft2 Fire Tests (Seawater only)
Extinguishment time (sec, max) 3.0% 50 45
Burnback (sec, min) 3.0% 360 420
*This proposal is based on a Dynax “Environmentally More Benign” 3% AFFF formulation containing 0.85%F (vs.
1.8%F for 3M Light Water FC-203CF)
Dynax Proposal for New MIL-F-Fire Performance SpecificationsBased on US Air Force SBIR Contract Report (1996)
Dynax Product Ionic Type Agent Application Guide
Fluorosurfactants AFFF AR-AFFF FFFP AR-FFFP
DX1030 Anionic • •
DX1040 Anionic • •
DX1080 Nonionic • • • •
DX1090 Nonionic • • • •
DX1025* Anionic • •
Foam Stabilizers
DX5011 Anionic • •
DX5022 Anionic • •
DX5065** Anionic • •
DX5066** Anionic • •
*Blends of fluorosurfactants **Blend of Fluorosurfactants and Foam Stabilizers
Dynax 6:2 Fluorotelomer Surfactants and Foam Stabilizers
4Th Reebok Foam Seminar, Bolton, UK 6 – 7 July 2009
Dynax Contact Info:
Chang Jho, 79 Westchester Avenue, Pound Ridge, NY 10576 USA
Tel: 914 764-0202 Fax: 914 -764-0533 e-mail: [email protected]
Thank you!
